Water-soluble fiber-reactive dyes, method for the production and use thereof

ABSTRACT

Dyes of general formula (I) wherein R 1 , R 2 , M, Y and x have the meaning cited in the description, the production and use thereof for dyeing or printing material containing hydroxy and/or carbonamide groups, preferably fiber material.

RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. 371)of PCT/EP03/04122 filed Apr. 22, 2003 which claims benefit to GermanApplication Serial no. 102 18 962.5 filed Apr. 27, 2002.

This invention relates to the field of fiber-reactive azo dyes.

Copper complexes of fiber-reactive monoazo compounds containing one ormore fiber-reactive groups are known for example from EP-A-526792,DE-A-4332255, DE-A-2049664, EP 0040806, EP-A-069376, DE-A-4039866,EP-A-281898, EP-A- 0345577, EP-A-395951 or EP 497174. However, they havecertain application defects, for example an excessive dependence of thecolor yield on varying parameters in the dyeing process, or aninadequate or unlevel color build-up on cotton, good color build-upresulting from the ability of a dye to provide a stronger dyeing whenused in a higher dye concentration in the dyebath. Moreover, these dyesexhibit unsatisfactory fixation yields, i.e., the portion of dyepermanently fixed to the material to be dyed is too low, especially atlow temperatures, and also unsatisfactory wash- and lightfastnesses.

However, it is important, for ecological and economic reasons, toprovide dyes having particularly high fixation yields in order that theportion of unfixed dye in the dyehouse effluent may be minimized.Moreover, dyes should always provide uniformly strong dyeings, ideallyregardless of changing dyeing parameters, for example the dyeingtemperature in the dyeing process. Furthermore, washfastness andlightfastness requirements are more stringent these days.

The present invention now provides dyes of the general formula (1) whichsurprisingly afford distinctly superior washfastnesses andlightfastnesses coupled with very good build-up. Moreover, these dyeshave higher fixation yields and a distinctly lower parameter dependencein dyeing. They are therefore also more compatible with other dyes whichfix at distinctly lower temperatures.

The invention accordingly provides dyes of the general formula (1):

where

-   -   M is hydrogen, alkali, ammonium or the equivalent of an alkaline        earth metal ion,    -   x is 0 or 1,    -   Y is —CH═CH₂ or —CH₂CH₂Z¹,        -   where        -   Z¹ is hydroxyl or an alkali-detachable group, and    -   R¹ is hydrogen or C₁–C₄-alkyl;    -   R² is a moiety of the general formulae (2), (3) or (4)

where

-   -   Y′ is —CH═CH₂ or —CH₂CH₂Z¹,        -   where    -   Z¹ is hydroxyl or an alkali-detachable group, and    -   T¹ is hydrogen, methyl, fluorine, chlorine or bromine,    -   T² is hydrogen, fluorine, chlorine or bromine with the proviso        that T² and T¹ are not both hydrogen;    -   T³ is hydrogen, methyl, fluorine, chlorine or bromine,    -   L is phenylene or naphthyl, which may be substituted by up to        two substituents selected from the group consisting of chloro,        bromo, hydroxyl, C₁ to C₄-alkyl especially methyl, ethyl, sulfo,        cyano, or else is a C₂ to C₆ alkylene which may be interrupted        by 1 to 2 hetero groups, such as for example oxo, thio, amino,        C₁–C₄-alkylamino.

L is preferably phenylene, ethylene, propylene and 3-oxopentylene.

(C₁–C₄)-Alkyl R¹ can be straight-chain or branched and is in particularselected from the group consisting of methyl, ethyl, n-propyl, i-propyl,n-butyl, i-butyl, sec-butyl and tert-butyl. Preference is given tomethyl and ethyl.

Examples of preferred R² radicals of the general formula (2) are:2,4-difluoropyrimidin-6-yl, 4,6-difluoropyrimidin-2-yl,5-chloro-2,4-difluoropyrimidin-6-yl,5-chloro-4,6-difluoropyrimidin-2-yl, 4,5-difluoropyrimidin-6-yl,5-chloro-4-fluoropyrimidin-6-yl, 2,4,5-trichloropyrimidin-6-yl,4,5-dichloropyrimidin-6-yl, 2,4-dichloropyrimidin-6-yl,4-fluoropyrimidin-6-yl, 4-chloropyrimidin-6-yl,2-fluoro-4-methylpyrimidin-6-yl.

Particular preference is given to R² being 2,4-difluoropyrimidin-6-yl or5-chloro-2,4-difluoropyrimidin-6-yl.

In the foregoing general formulae and also in the subsequent generalformulae, the individual symbols, whether they bear identical ordifferent designations within any one general formula, can have meaningsunder their definition which are mutually identical or different.

The dyes of the general formula (1) can possess different fiber-reactivegroups —SO₂Y and —SO₂Y′ within the meaning of Y and Y′ respectively.Examples of alkali-eliminable substituents Z¹ in the β-position of theethyl group of Y or Y′ are halogen atoms, such as chlorine and bromine,ester groups of organic carboxylic and sulfonic acids, such asalkylcarboxylic acids, optionally substituted benzenecarboxylic acidsand optionally substituted benzenesulfonic acids, such as the groupsalkanoyloxy of 2 to 5 carbon atoms, of which in particular acetyloxy,benzoyloxy, sulfobenzoyloxy, phenylsulfonyloxy and tolylsulfonyloxy,further acidic ester groups of inorganic acids, as of phosphoric acid,sulfuric acid and thiosulfuric acid (phosphato, sulfato and thiosulfatogroups), similarly dialkylamino groups having alkyl groups of 1 to 4carbon atoms each, such as dimethylamino and diethylamino. Moreparticularly, the fiber-reactive groups —SO₂Y and —SO₂Y′ can be firstvinylsulfonyl groups and secondly groups —CH₂CH₂Z¹, preferablyβ-chloroethyl and especially β-sulfatoethylsulfonyl groups.

The groups sulfo, carboxyl, phosphato and sulfato include not only theiracid form but also their salt form. Accordingly, sulfo groups are groupsconforming to the general formula —SO₃M, carboxyl groups are groupsconforming to the general formula —COOM, phosphato groups are groupsconforming to the general formula —OPO₃M₂ and sulfato groups are groupsconforming to the general formula —OSO₃M in each of which M is asdefined above.

The dyes of the general formula (1) according to the invention arepreparable for example by conventional diazotization of the aromaticamines of the general formula (8)

where M, Y and x are each as defined above,and coupling to a coupling component of the general formula (9)

where T¹, T², T³ and M are each as defined above, and subsequentcoppering in a manner familiar to one skilled in the art to prepare thedyes of the formula (1) according to the invention.

Diazotizable amines having complexing radicals of the general formula(8) are for example 3-amino-4-hydroxyphenyl β-hydroxyethyl sulfone,3-amino-4-hydroxyphenyl β-sulfatoethyl sulfone, 3-amino-4-hydroxyphenylvinyl sulfone, 4-amino-5-hydroxyphenyl β-hydroxyethyl sulfone,4-amino-5-hydroxyphenyl β-sulfatoethyl sulfone, 4-amino-5-hydroxyphenylvinyl sulfone, 3-amino-4-hydroxy-5-sulfophenyl β-sulfatoethyl sulfone,3-amino-4-hydroxy-5-sulfophenyl vinyl sulfone.

The coupling components of the general formula (9) are obtainable byconventional condensation of compounds of the general formula (10)

where R¹ and M are each as defined above, with compounds of the generalformulae (11), (12) or (13)

where T¹, T², T³, L and Y′ are each as defined above and X is fluorine,chlorine or bromine. When R² is a group of the general formula (2), thedye can contain two isomers, depending on the meaning of thesubstituents.

Compounds of the general formula (10) are for example2-amino-5-hydroxynaphthalene-7-sulfonic acid,2-N-methylamino-5-hydroxynaphthalene-7-sulfonic acid.

Compounds of the general formula (11) are for example2,4,6-trifluoropyrimidine; 4,5,6-trifluoropyrimidine;2,4,5,6-tetrafluoropyrimidine; 4,6-difluoropyrimidine;2,4,5,6-tetrachloropyrimidine; 2,4,6-trichloropyrimidine;2,4,6-tribromopyrimidine; 2,4,6-trifluoro-5-chloropyrimidine;5-methyl-2,4,6-trichloropyrimidine, 4,6-difluoro-5-chloro-pyrimidine.

Compounds of the general formula (12) are for example3-chloroethylsulfonylbenzoyl chloride, 2-chloroethylsulfonylpropionylchloride.

Compounds of the general formula (13) are2,3-dichloroquinoxaline-5-carbonyl chloride and2,3-dichloroquinoxaline-6-carbonyl chloride.

Alternatively, the diazotization of the compounds of the general formula(8) and coupling onto compounds of the formula (10) can be carried outfirst, followed by a subsequent coppering, which in turn is followed bythe condensation with a compound of the general formula (11), (12) or(13), or the conventional diazotization of the aromatic amines of thegeneral formula (8)

where M, Y and x are each as defined above, and coupling onto a couplingcomponent of the general formula 10 are carried out first, followed bythe condensation with a compound of the general formula (11), (12) or(13), which in turn is followed by coppering with copper sulfatepentahydrate in a manner familiar to one skilled in the art.

The separation and isolation, from the aqueous synthesis solutions, ofthe compounds of the general formula (1) according to the invention canbe effected according to generally known methods for water-solublecompounds, for example by precipitating from the reaction medium bymeans of an electrolyte, such as sodium chloride or potassium chloridefor example, or by evaporating the reaction solution itself, for exampleby spray drying. In the latter case, it is frequently advisable first toprecipitate any sulfate in the solutions as calcium sulfate and removeit by filtration.

The dyes of the invention can be present as a preparation in solid or inliquid (dissolved) form. In solid form, they generally include theelectrolyte salts customary for water-soluble and especially forfiber-reactive dyes, such as sodium chloride, potassium chloride andsodium sulfate, and may further include the auxiliaries customary incommercial dyes, such as buffer substances capable of setting a pH inaqueous solution between 3 and 7, such as sodium acetate, sodium borate,sodium bicarbonate, sodium dihydrogenphosphate, sodium tricitrate anddisodium hydrogenphosphate, or small amounts of siccatives; if they arepresent in a liquid, aqueous solution (including the presence ofthickeners of the type customary in print pastes), they may also includesubstances which ensure a long life for these preparations, for examplemold preventatives.

In general, the dyes of the invention are present as dye powderscontaining 10 to 80% by weight, based on the dye powder or thepreparation, of an electrolyte salt which is also referred to as astandardizing agent. These dye powders may additionally include theaforementioned buffer substances in a total amount of up to 10% byweight, based on the dye powder. If the dyes of the invention arepresent in aqueous solution, the total dye content of these aqueoussolutions will be up to about 50% by weight, for example between 5 and50% by weight, and the electrolyte salt content of these aqueoussolutions will preferably be below 10% by weight, based on the aqueoussolution; the aqueous solutions (liquid preparations) may include theaforementioned buffer substances in an amount which is generally up to10% by weight, preferably up to 2% by weight.

The dyes of the invention have useful application properties. They areused for dyeing or printing hydroxyl- and/or carboxamido-containingmaterials, for example in the form of sheetlike structures, such aspaper and leather or of films, for example composed of polyamide, or inbulk, as for example of polyamide and polyurethane, but especially fordyeing or printing these materials in fiber form. Similarly, the as-synthesized solutions of the dyes of the invention, if appropriate afteraddition of a buffer substance and if appropriate after concentrating ordiluting, can be used directly as liquid preparation for dyeing.

The present invention thus also relates to the use of the dyes of theinvention for dyeing or printing these materials and to processes fordyeing or printing these materials in a conventional manner, by usingdyes of the invention as a colorant. The materials are preferablyemployed in the form of fiber materials, especially in the form oftextile fibers, such as woven fabrics or yarns, as in the form of hanksor wound packages.

Hydroxyl-containing materials are those of natural or synthetic origin,for example cellulose fiber materials or their regenerated products andpolyvinyl alcohols. Cellulose fiber materials are preferably cotton, butalso other vegetable fibers, such as linen, hemp, jute and ramie fibers;regenerated cellulose fibers are for example staple viscose and filamentviscose.

Carboxamido-containing materials are for example synthetic and naturalpolyamides and polyurethanes, especially in the form of fibers, forexample wool and other animal hairs, silk, leather, nylon-6,6, nylon-6,nylon-11 and nylon-4.

The dyes of the invention can be applied to and fixed on the substratesmentioned, especially the fiber materials mentioned, by the applicationtechniques known for water-soluble dyes, especially fiber-reactive dyes.

For instance, on cellulose fibers they produce by the exhaust methodfrom a long liquor using various acid-binding agents and optionallyneutral salts, such as sodium chloride or sodium sulfate, dyeings havingvery good washfastnesses. Application is preferably from an aqueous bathat temperatures between 40 and 105° C., optionally at a temperature ofup to 130° C. under superatmospheric pressure, and optionally in thepresence of customary dyeing auxiliaries. One possible procedure is tointroduce the material into the warm bath and to gradually heat the bathto the desired dyeing temperature and to complete the dyeing process atthat temperature. The neutral salts which accelerate the exhaustion ofthe dyes may also, if desired, only be added to the bath after theactual dyeing temperature has been reached.

The padding process likewise provides excellent color yields and verygood color build-up on cellulose fibers, the dyes being allowed tobecome fixed on the material by batching at room temperature or atelevated temperature, for example at up to 60° C., by steaming or usingdry heat in a conventional manner.

Similarly, the customary printing processes for cellulose fibers, whichcan be carried out either single-phase, for example by printing with aprint paste comprising sodium bicarbonate or some other acid-bindingagent and by subsequent steaming at 100 to 103° C., or two-phase, forexample by printing with a neutral or weakly acidic print color andsubsequent fixation either by passing the printed material through a hotelectrolyte-comprising alkaline bath or by overpadding with an alkalineelectrolyte-comprising padding liquor with subsequent batching of thealkali-overpadded material or subsequent steaming or subsequenttreatment with dry heat, produce strong prints with well-definedcontours and a clear white ground. The appearance of the prints is notgreatly affected by variations in the fixing conditions.

When fixing by means of dry heat in accordance with the customarythermofix processes, hot air from 120 to 200° C. is used. In addition tothe customary steam at 101 to 103° C., it is also possible to usesuperheated steam and high-pressure steam at temperatures of up to 160°C.

The acid-binding agents which effect the fixation of the dyes of theinvention on the cellulose fibers include for example water-solublebasic salts of the alkali metals and likewise alkaline earth metals ofinorganic or organic acids or compounds which liberate alkali in theheat. Especially suitable are the alkali metal hydroxides and alkalimetal salts of weak to medium inorganic or organic acids, the preferredalkali metal compounds being the sodium and potassium compounds. Suchacid-binding agents include for example sodium hydroxide, potassiumhydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate,sodium formate, sodium dihydrogenphosphate, disodium hydrogenphosphate,sodium trichloroacetate, waterglass or trisodium phosphate.

The cellulose dyeings obtained following the customary aftertreatment byrinsing to remove unfixed dye portions exhibit very good dye propertiesand provide by the application and fixing methods customary in the artfor fiber-reactive dyes strong olive dyeings and prints having very goodfastness properties, especially very good wash-, light-, alkali-, acid-,water-, seawater-, perspiration- and rubfastnesses, on the materialsmentioned in the description, such as cellulose fiber materials,especially cotton and viscose. The dyeings are further notable for theirhigh degree of fixation and good build-up on cellulose materials. Ofparticular advantage is the good washfastness of the dyeings, the highfixation value and the low temperature dependence compared with theprior art.

Furthermore, the dyes of the invention can also be used for thefiber-reactive dyeing of wool. Moreover, wool which has been given anonfelting or low-felting finish (cf. for example H. Rath, Lehrbuch derTextilchemie, Springer-Verlag, 3rd Edition (1972), p. 295–299,especially the finish by the Hercosett process (p. 298); J. Soc. Dyersand Colourists 1972, 93–99, and 1975, 33–44) can be dyed with very goodfastness properties.

The process of dyeing on wool is here carried out in a conventionalmanner from an acidic medium. For instance, acetic acid and/or ammoniumsulfate or acetic acid and ammonium acetate or sodium acetate may beadded to the dyebath to obtain the desired pH. To obtain a dyeing ofacceptable levelness, it is advisable to add a customary leveling agent,for example on the basis of a reaction product of cyanuric chloride with3 times the molar amount of an aminobenzenesulfonic acid and/or of anaminonaphthalenesulfonic acid or on the basis of a reaction product offor example stearylamine with ethylene oxide. For instance, the dyes ofthe invention are preferably subjected to the exhaust process initiallyfrom an acidic dyebath having a pH of about 3.5 to 5.5 under pH controland the pH is then, toward the end of the dyeing time, shifted into theneutral and optionally weakly alkaline range up to a pH of 8.5 to bringabout, especially for very deep dyeings, the full reactive bond betweenthe dyes of the invention and the fiber. At the same time, the dyeportion not reactively bound is removed.

The procedure described herein also applies to the production of dyeingson fiber materials composed of other natural polyamides or of syntheticpolyamides and polyurethanes. In general, the material to be dyed isintroduced into the bath at a temperature of about 40° C., agitatedtherein for some time, the dyebath is then adjusted to the desiredweakly acidic, preferably weakly acetic acid, pH and the actual dyeingis carried out at a temperature between 60 and 98° C. However, thedyeings can also be carried out at the boil or in sealed dyeingapparatus at temperatures of up to 106° C. Since the water solubility ofthe dyes of the invention is very good, they can also be used withadvantage in customary continuous dyeing processes. The dyes of theinvention dye the materials mentioned in ruby red shades.

The examples hereinbelow serve to illustrate the invention. Parts andpercentages are by weight, unless otherwise stated. The compoundsdescribed in the examples in terms of a formula are partly indicated inthe form of free acids; in general these compounds are prepared andisolated in the form of their salts preferably sodium or potassiumsalts, and used for dyeing in the form of their salts. The startingcompounds mentioned in the following examples, especially tableexamples, can similarly be used in the synthesis in the form of the freeacid or in the form of their salts, preferably alkali metal salts, suchas lithium, sodium or potassium salts.

EXAMPLE 1

377 parts of 2-amino 4-sulfatoethylsulfonyl-6-phenolsulfonic acid arediazotized with sodium nitrite and coupled at pH 6–7 onto 353 parts ofthe condensation product of 2-amino-5-hydroxynaphthalene-7-sulfonic acidand 2,4,6-trifluoropyrimidine and subsequently reacted with 245 parts ofcopper sulfate pentahydrate. The red dye obtained of the formula A (oneof the isomers is indicated as a free acid)

is salted out with sodium chloride, filtered off and dried at 50° C.under reduced pressure. The dye produces ruby red dyeings and prints oncotton which have very good fastnesses, especially a very goodlightfastness.

EXAMPLE 2

377 parts of 2-amino 4-sulfatoethylsulfonyl-6-phenolsulfonic acid arediazotized with sodium nitrite and coupled onto 239 parts of2-amino-5-hydroxy naphthalene-7-sulfonic acid and subsequently reactedwith 250 parts of copper sulfate pentahydrate. The red dye obtained ofthe formula B

is optionally salted out with sodium chloride, filtered off and dried at50° C. under reduced pressure. The dye produces ruby red dyeings andprints on cotton which have good fastnesses and are stable to oxidativeinfluences.

Reaction of dye B with 2,4,6-trifluoropyrimidine gives the dye of theformula (A).

EXAMPLE 3

Proceeding as described in Examples 1 or 2 and using2-N-methylamino-5-hydroxynaphthalene-7-sulfonic acid as a couplingcomponent affords dye C

which has excellent fastnesses.

The table which follows describes further dyes according to theinvention which can be prepared along the lines of the above examples, Xbeing fluorine, chlorine or bromine.

Example number Compound of formula (11), (12) or (13) Compound offormula (10) Compound of formula (8) Hue 4

ruby red 5

ruby red 6

ruby red 7

ruby red 8

ruby red 9

ruby red 10

ruby red 11

ruby red 12

ruby redDyeing Example:

4 parts of the dye of Example 2 are dissolved in 200 parts of water. 20parts of sodium chloride, 5 parts of aqueous sodium hydroxide solutionand 20 parts of cotton fabric are added before heating to 60° C. in adyeing apparatus over 20 min. At 60° C., dyeing is carried out for 45min. The cotton fabric is subsequently rinsed with water and diluteacetic acid and dried. This gives a ruby red dyeing having very goodfastness properties.

1. Dyes of the general formula (1):

where M is hydrogen, alkali, ammonium or the equivalent of an alkalineearth metal ion, x is 0 or 1, Y is —CH═CH₂ or —CH₂CH₂Z¹, where Z¹ ishydroxyl or an alkali-detachable group, and R¹ is hydrogen orC₁–C₄-alkyl; R² is a moiety of the general formulae (2), (3) or (4)

where T¹ is hydrogen, methyl, fluorine, chlorine or bromine, T² ishydrogen, fluorine or chlorine with the proviso that T² and T¹ are notboth hydrogen; T³ is hydrogen, methyl, fluorine, chlorine or bromine, Y′is —CH═CH₂ or —CH₂CH₂Z¹, where Z¹ is hydroxyl or an alkali-detachablegroup, and L is phenylene or naphthylene, which may be substituted by upto two substituents selected from the group consisting of chloro, bromo,hydroxyl, C₁ to C₄-alkyl, sulfo, cyano, or L is a C₂ to C₆ alkylenewhich is optionally interrupted by 1 to 2 hetero groups.
 2. Dyes asclaimed in claim 1, wherein R² is a moiety of the general formula (2)

where T¹, T² and T³ are each as defined in claim
 1. 3. Dyes as claimedin claim 1, wherein x is 1 and the SO₂Y group is meta to the azo group.4. Dyes as claimed in claim 1, wherein R² is difluoropyrimidyl.
 5. Aprocess for preparing compounds as claimed in claim 1 which comprisesdiazotizing the aromatic amines of the general formula (8)

where M, Z, Y and x are each as defined in claim 1, and coupling onto acoupling component of the general formula (9)

where T¹, T², T³ and M are each as defined in claim 1, followed by asubsequent coppering with copper sulfate pentahydrate.
 6. A process forpreparing compounds as claimed in claim 1 which comprises diazotizingthe aromatic amines of the general formula (8)

where M, Z, Y and x are each as defined in claim 1, and coupling onto acoupling component of the general formula (10)

where R¹ and M are each as defined in claim 1, followed by subsequentcoppering with copper sulfate pentahydrate and a condensation with afiber-reactive group of the general formula (11), (12) or (13)

where T¹, T², T³, L and Y′ are each as defined in claim 1 and X isfluorine, chlorine or bromine.
 7. A process for preparing compounds asclaimed in claim 1 which comprises diazotizing the aromatic amines ofthe general formula (8)

where M, Z, Y and x are each as defined in claim 1, followed by couplingonto a coupling component of the general formula (10)

where R¹ and M are each as defined in claim 1, and a condensation with afiber-reactive group of the general formula (11), (12) or (13)

where T¹, T², T³, L and Y′ are each as defined in claim 1 and X isfluorine, chlorine or bromine and subsequent coppering with coppersulfate pentahydrate.
 8. A process for dyeing or printing hydroxyl-and/or carboxamido-containing material which comprises applying one ormore dyes as claimed in claim 1 in dissolved form to the material andfixing the dye or dyes on the material by means of (a) heat or (b) withthe aid of an alkaline agent or (c) by means of heat and with the aid ofan alkaline agent.
 9. A dye preparation comprising the dyes as claimedin claim
 1. 10. Dyes as claimed in claim 2, wherein L is phenylene ornaphthylene, which may be substituted by up to two substituents selectedfrom the group consisting of chloro, bromo, hydroxyl, methyl, ethyl,sulfo, cyano, or L is a C₂ to C₆ alkylene which is optionallyinterrupted by 1 to 2 hetero groups selected from the group consistingof oxo, thio, amino and C₁–C₄-alkylamino.
 11. Dyes as claimed in claim10, wherein x is 1 and the SO₂Y group is meta to the azo group.
 12. Dyesas claimed in claim 11, wherein R² is difluoropyrimidyl.
 13. The processas claimed in claim 8, wherein the material is a fiber material. 14.Dyes as claimed in claim 2, wherein L is phenylene, ethylene, propyleneor oxopentylene.
 15. Dyes as claimed in claim 1, wherein R² is5-chloro-2,4-difluorpyrimidin-6-yl.
 16. The process as claimed in claim5, wherein the aromatic amines of formula (8) are3-amino-4-hydroxyphenyl β-hydroxyethyl sulfone, 3-amino-4-hydroxyphenylβ-sulfatoethyl sulfone, 3-amino-4-hydroxyphenyl vinyl sulfone,4-amino-5-hydroxyphenyl β-hydroxyethyl sulfone, 4-amino-5-hydroxyphenylβ-sulfatoethyl sulfone, 4-amino-5-hydroxyphenyl vinyl sulfone,3-amino-4-hydroxy-5-sulfophenyl β-sulfatoethyl sulfone, or3-amino-4-hydroxy-5-sulfophenyl vinyl sulfone.
 17. The process asclaimed in claim 6, wherein said aromatic amines of formula (8) are3-amino-4-hydroxyphenyl β-hydroxyethyl sulfone, 3-amino-4-hydroxyphenylβ-sulfatoethyl sulfone, 3-amino-4-hydroxyphenyl vinyl sulfone,4-amino-5-hydroxyphenyl β-hydroxyethyl sulfone, 4-amino-5-hydroxyphenylβ-sulfatoethyl sulfone, 4-amino-5-hydroxyphenyl vinyl sulfone,3-amino-4-hydroxy-5-sulfophenyl β-sulfatoethyl sulfone, or3-amino-4-hydroxy-5-sulfophenyl vinyl sulfone; said coupling componentof the general formula (10) are 2-amino-5-hydroxynaphthalene-7-sulfonicacid or 2-N-methylamino-5-hydroxynaphthalene-7-sulfonic acid;fiber-reactive group of the general formula (11) are2,4,6-trifluoropyrimidine; 4,5,6-trifluoropyrimidine;2,4,5,6-tetrafluoropyrimidine; 4,6-difluoropyrimidine;2,4,5,6-tetrachloropyrimidine; 2,4,6-trichloropyrimidine;2,4,6-tribromopyrimidine; 2,4,6-trifluoro-5-chloropyrimidine;5-methyl-2,4,6-trichloropyrimidine or 4,6-difluoro-5-chloro-pyrimidine;fiber-reactive group of the general formula (12) are3-chloroethylsulfonyl-benzoyl chloride or 2-chloroethylsulfonylpropionylchloride; and fiber-reactive group of the general formula (13) are2,3-dichloroquinoxaline-5-carbonyl chloride or2,3-dichloroquinoxaline-6-carbonyl chloride.
 18. The process as claimedin claim 7, wherein said aromatic amines of formula (8) are3-amino-4-hydroxyphenyl β-hydroxyethyl sulfone, 3-amino-4-hydroxyphenylβ-sulfatoethyl sulfone, 3-amino-4-hydroxyphenyl vinyl sulfone,4-amino-5-hydroxyphenyl β-hydroxyethyl sulfone, 4-amino-5-hydroxyphenylβ-sulfatoethyl sulfone, 4-amino-5-hydroxyphenyl vinyl sulfone,3-amino-4-hydroxy-5-sulfophenyl β-sulfatoethyl sulfone, or3-amino-4-hydroxy-5-sulfophenyl vinyl sulfone; said coupling componentof the general formula (10) are 2-amino-5-hydroxynaphthalene-7-sulfonicacid or 2-N-methylamino-5-hydroxynaphthalene-7-sulfonic acid;fiber-reactive group of the general formula (11) are2,4,6-trifluoropyrimidine; 4,5,6-trifluoropyrimidine;2,4,5,6-tetrafluoropyrimidine; 4,6-difluoropyrimidine;2,4,5,6-tetrachloropyrimidine; 2,4,6-trichloropyrimidine;2,4,6-tribromopyrimidine; 2,4,6-trifluoro-5-chloropyrimidine;5-methyl-2,4,6-trichloropyrimidine or 4,6-difluoro-5-chloro-pyrimidine;fiber-reactive group of the general formula (12) are3-chloroethylsulfonyl-benzoyl chloride or 2-chloroethylsulfonylpropionylchloride; and fiber-reactive group of the general formula (13) are2,3-dichloroquinoxaline-5-carbonyl chloride or2,3-dichloroquinoxaline-6-carbonyl chloride.